Mineral oil composition and improving agent therefor



Patented Aug. 10, 1943 MINERAL OIL COMPOSITION AND IltlPROV- ING AGENT THEREFOR Orland M. Reifi, Woodbury, N. 1., assignor to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York No Drawing. Application April 20, 1940,

Serial No. 330,693

13 Claims.

, This invention has to do in a general way with mineral oil compositions and is more particularly related to mineral oil compositions of the lubricant type to which an agent has been added in a minor proportion for the purpose of improving the oil in certain respects. It is an object of this invention toprovide a novel class of mineral oil addition-agents which will improve one or more important properties of a mineral oil fraction. It is a further object to provide mineral oil compositions containing such improving agents. i

In copending application'Serial No. 226,911 (Patent 2,198,293), filed August 26, 1938, in which 'I am a coinventor, there are described as mineral oil addition agents a general class of alkylsubstituted aryl ether acids which are characterized by the presence of a wax- (or heavy alkyl-) substituted aryl nucleus, such addition agents being multifunctional in that they are effective to reduce the pour point and improve the viscosity index of the oil to which they are added. The present invention is predicated upon the discovery that the sulfur derivatives or, more specifically, the sulfides (monosulfides and polysulfides) of alkyl-substituted aryl ether acids of the type disclosed in the aforesaid application are improved in certain respects over the corresponding alkylated aryl ether acids from which such sulfides are obtained. In addition to the sulfides or sulfur derivatives my invention also contemplates the corresponding derivatives of the related elements, selenium and tellurium.

More specifically, the present invention is concerned with condensation compounds of sulfur, selenium; or'tellurium corresponding in general to the alkyl-substituted aryl ether acids disclosed in the aforesaid copending application. The addition agents of the present invention, like those of this last-mentioned copending application, are characterized by the presence of an aromatic nucleus in which at least one nuclear hydrogen 'atom is substitutedwith an oil-solubilizing alkyl lenium, and tellurium. Through the introduc tion of sulfur, for example, in the manner for manners to be hereinafter described, I obtain what may be broadly termed a sulfide of an alkyl-substituted aryl ether carboxylic acid.

This general class of sulfides of alkyl-substituted aryl ether acids distinguishes over the ment of acidity in certain types of oils and un H corresponding alkylated aryl ether acids disclosed in the aforesaid application in that the sulfides possess the property of retarding the deleterious effects of oxidation in the oil to which they are added. In the preferred multifunctional class of the.addition agents con templated herein I have found thatithe sulfides, in general, possess improved pour depressant and viscosity index improving properties in addition to the antioxidant properties just referred to. The improved antioxidantproperties are particularly significantin retarding the developdercertain conditions of use.

The property of Oil-miscibility-that is, of remaining uniformly suspended in the oil under normal conditions of handling and 'use-is imparted to the condensation products contemplated herein by the alkyl substituent onthe characterizingaryl nucleus. This substitue'nt, therefore, should be derived from an aliphatic hydrocarbon of sufficient solubilizing value to render the condensation product oil-miscible. For obtaining the preferred product having multifunctional properties, the alkyl substituent should correspond to an aliphatic hydrocarbon having at least twenty carbon atoms or should be derived from an aliphatic material or mix-" ture of aliphatic compounds predominantly comprised of compounds having at least twenty carbon atoms. A petroleum wax such as paraffin wax constitutes a preferred source for these socalled heavy alkyl substituents of the latter type.

and for'that reason the preferred multifunctional'compounds may be hereinafter designated as wax,-substituted. It is to be understood, however, that the term wax as used in this regard is not restricted to substituent groups derived from petroleum wax but is intendedto include substituent groups derived from any aliphatic hydrocarbon or mixture thereof orv any predominantly aliphatic material which is in character or constituents similar' to the constituents of petroleum wax.

The condensation-products of alkyl-substituted aryl ether acids of the type contemplated herein may be characterized by the general formula:

in which T represents a monocyclic or polycyclic aromatic nucleus; 2 represents sulfur, selenium. or tellurium; and n'represents a whole number from one to four. Thegroup O.Z.COOH represents what I may term an ether carboxylic' acid group wherein Z represents an aliphatic, alicyclic,

at least one alkyl group having at least twenty carbon atoms hereinabove identified as a "wax group. In addition to the oil-solubillzing alkyl group (R), the characterizing aryl nucleus may contain residual hydrogen, a part or all of which may in turn be substituted with substituents having a positive or negative or neutral oil-solubilizing effect. Such residual hydrogen or substituents are indicated by Yb in the general formula, wherein Y may be defined as selected from the group consisting of hydrogen, hydroxyl, ester (organic or inorganic acyl group), keto, alkoxy, alkyl sulfide, aryl sulfide, aroxy, ether alcohol, aldehyde, thioaldehyde, oxime, amido (organic or inorganic acyl group), thioamido, carbamido, aralkyl, aryl, alkaryl, halogen, nitr'oso, amino, nitrosamlno, amidino, imino, N-thio, diazo, hydrazine, cyano, azoxy, azo, and hydrazo radicals;

and b represents the number of Y' and is equal to zero or a whole number corresponding to available hydrogens on the nucleus T not substituted with R, O.Z.COOH and En.

As aforesaid, Z may be an aromatic nucleus, and in that event this aryl nucleus may have R and Y substituents and the condensation with the linkage En may take place between the aryl nucleus or nuclei of such a Z group. The foregoing general formula is intended to include such modified derivatives. When Z is aliphatic, the Y type of substituents may also be present, excepting those of strictly aromatic origin, such as those resulting from diazotization, for instance.

As aforesaid, the aryl nucleus 'I' may be monoor poly-cyclic, corresponding, for example, to phenol, naphthol, anthrol, and their derivatives. A typical condensation product in which the alkylated aryl ether acid groups are derived from alkylated phenol may, in its simplest form, be represented by the general formula:

o.z.coon 0.Z.COH

III

O.Z.COOH O.Z.COOH O.Z.COOH

n R it Also, where synthesis of the condensation product employs as an initial reactant a wax-substituted phenol obtained by the Friedel-Crafts condensation of phenol with a halogenated aliphatic compound containing at least twenty carbon atoms or a mixture, such as petroleum wax, predominantly comprised of such high molecular weight aliphatic hydrocarbons, thi condensation Sal or compounds of the formula O.Z. COOH Z.COOH

01.00011 ng-o in which the chains represent the aliphatic hydrocarbon' group R of general Formula I.

The foregoing discussion pertaining to Formulae II to V is not intended as a development of the specific molecular composition or structure of condensation products constituting the mineral oil addition agents contemplated herein but is merely intended as indicative of the possible composition of such addition agents. These addition agents may be broadly characterized as the sulfides (or the corresponding selenides or tellur- 40 ides) of alkylated aryl ether carboxylic acids.

The sulfur condensation products may also be characterized as alkylated-aroxy aliphatic carboxylic acid sulfides and alkylated-aroxy aromatic carboxylic acid sulfides.

As aforesaid, the term sulfide as used herein ,is inclusive of the monosulfides, disulfides, trisulfides, tetrasulfides, etc.--that is, it includes both monosulfides and polysulfidesand it is also intended to include such polymers and related derivatives as may be formed by the hereinafter described procedures employed to illustrate the synthesis of the addition agents contemplated herein. It is also pointed out that the so-called polymer products typified by Formulae III to V are included under general Formula I since they are characterized by having therein at least one grouping typified by general Formula I.

The sulfur derivatives or sulfides of the alkylated aryl ether acid are the preferred class of condensation products contemplated herein, and for that reason the invention will be specifically described in connection with these derivatives although, as aforesaid, the corresponding selenides and tellurides are contemplated as coming within the scope of the broad inventive concept.

One general procedure for synthesizing the sulfides of alkylated aryl ether acids is to react the corresponding alkylated aryl ether acid with a sulfur halide. Another procedure of this type involves condensation of the alkali metal carboxylates of the alkylated aryl ether acids with a sulfur halide, whereby sulfides of alkylated aryl ether acids of lighter-color may be obtained.

Another desirable procedure'consists in conversion of a wax-phenol or wax-alkali phenate to the wax-hydroxy-aryl sulfide, followed by introduction of the ether acid group. When Z is aromatic, however, the preceding procedures are preferred.

In the event sulfur dichloride (S012) is used in the general procedure described above, the condensation product will be in the nature of a monosulfide (or polymer thereof) sulfur monochloride will yield the corresponding disulfide (or polymer thereof), and of course, a mixtur of sulfur halides may be employed to obtain a mixture of sulfides. Elementary sulfur may be employed as the condensation reagent, but this is not considered the most desirable procedure.

Sulfur derivatives of higher sulfur content may be obtained by reacting a condensation product having the disulfide linkage with sulfur or with alkali polysulfides or with an alkyl tetrasulfide. Such higher sulfur derivatives may also be obtained by first reducing the disulfide to form a thio-phenol or aryl mercaptan of the alkylated aryl ether acid andthen reacting the aryl mercaptan derivative with sulfur dichloride (to form the trisulfide) or with sulfur monochloride (to form the tetrasulfide).

The alkylated aryl ether acids and their alkali metal saltsused in preparing th sulfides may be obtained in various ways. "The details in desirable procedures for preparing the alkylated aryl ether acids are described in the aforesaid copending application 226,911. A typical procedure for forming the alkali carboxylates and the corresponding alkylated aryl' ether acids involves the following steps.

(1) A hydroxyaromatic compound such as phe-- n01 is reacted with a halogenated high molecular weight aliphatic hydrocarbon, or a mixture predominantly comprised of these high molecular weight aliphatic compounds such as chlorinated petroleum wax, in the presence of a Friedel- Crafts catalyst such as anhydrous, aluminum chloride. The wax may be chlorinated to a-chlorine content of from about per cent to about per cent, and the ratio of chlorinated wax to phenol in the reaction mixture. may, for example, be such that there are three atomic propor-' tions of chlorine present in chlorwax of 16 per cent chlorine content togone molecular proportion of phenol. The reaction is carried out at elevated temperature, preferably not to exceed The "alkylated alkali metal phenate can be prepared more conveniently, however. by ma tion of the alkylated phenol with sodium alcos holate, suchas sodium butylate, by heating the mixture to about 300 F. and allowing the alcohol to distill.

(3) The alkylated aryl metal oxide or Waxalkall phenate obtained by the foregoing step may be converted to a wax-phenoxy aliphatic acid alkali metal salt byv reaction of the phenate with the alkali salt of a chlor (monoor polybasic) aliphatic acid. Alkali salts of dlaryl ether acids (wax-aroxy aromatic acid alkali metal salts) can be obtained by reacting the wax-al kali phenate with a brom-aryl alkali carboxylate in the presence. of a small percentage of powdered copper as a catalyst. the reaction mixture being heated to a temperature in the neighborhood of 400 F. The alkali metal salts 'of the alkylated aryl ether acids can be converted to the corresponding acids by acidifying with a mineral acid such as HCl. v

When it is desired to obtain a compound or condensation product in which the characterizing aryl nucleus contains. in addition to or in.-

stead of residual hydrogen, a substituent of the i type classified in general Formula I as Yb, it is pointed out that with the exception of substituents suchas aralkyl, aryl, alkaryl, halogen, hydroxyl, and'aroxy, such Y groups are introduced after alkylation (step 1 above) and generally before introduction of the ether acid group. The

usual methods for introduction of these substituents into non-alkylated hydroxyaromatic compounds may be employed in connection-with the alkylated or wax-substituted hydroxyaromatic compounds obtained in step 1, To those skilled in the art it will be apparent that the Y substituents are mainly derivatives of phenolic (-OH) groups, amino groups, aldehyde and keto groups, and carboxyl groups. Methods for the introduction of such base substituents along with -Z.COOH groups will be apparent from methods described in the aforesaid copending application.

' The foregoing is merely a general description of a typical procedure which may be employed to obtain aninitial reactant for making the sulwhich may be used as the starting material in similar expression, the first numeral (3) in the parenthesis indicating the ratio of chlorine (atomic proportions) to one mol of phenol in the reaction mixture and the second numeral (16) indicating the chlorine content of the chlorinated wax.

(2) An alkylated phenol of the type obtained according to the foregoing step is converted to the corresponding wax-substituted alkali metal phenate by a suitable procedure such as by reaction with metallic sodium (or potassium) at elevated temperature, in the neighborhood of 500 F., in the presence of a non-oxidizing gas. The mixture should be rapidly stirred to produce finely divided sodium and thereby accelerate the reaction. The proportions of the reactants should be such that there is sufficient sodium present to substitute the hydroxyl hydrogen.

step 1 are: phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydro-xy-diphenyl, ben- -zylphenol, phenyl-ethyl-phenol, phenol resins,

methyl-hydroxydiphenyl, alpha and beta napht'hol, tolyl naphthol, anthrol and the like, with special preference given to phenol (hydroxybenzene) and alpha and beta naphthol. The chloraliphatic material employed in step one should contain, or should be predominantly comprised of compounds containing. at least twenty carbon atoms to obtain the preferred mult i-f-unctional products. A chlorinated petroleum wax such as parafiln wax having a melting point not substantially less than about F. is a preferred material to use in this reaction. These chlorine .ated aliphatic reactants may, however, be pure high molecular weight compounds capable of imparting oil-miscibility to the product, but preference is given to mixed high molecular weight hydrocarbons typified by those which characterize the heavier products of petroleum such as heavy petroleum oils of the lubricant type, petrolatum and crystalline petroleum wax or other pre- -dominantly aliphatic materials which will result in- "relatively 'longchain aliphatic substituents.

As an'alternativeprocedure for eifecting a1- kylation of *the-aryl nucleus I- may employ un- -'-'saturated aliphatic hydrocarbons,"preferably of high molecular weight, such as eicosylene, cero- "tene, melene, etc.,'using HzSO4,'BFa or AlCla as a catalyst. Other sources for the heavy .alkyl subs'tituents-are higher alcohols, preferably of at'leas't"20 carbon chain lengths, such as ceryl I alcohol, myricylalcohol, etc. High molecular 'wei'ght al'cohols can be condensed with phenols 'fdir'ectl-y' in -the presence of H2804 or AlCla as a "catalyst,'butit is'preferred-to convert the alcof hol to' the corresponding halide"(or 'polyhalide) and then condense thesame with the hydroxyaromatic compoundby the -Friedel-Crafts reaction;' I

Examples of halogenated organic acids which msybe used "(as their alkali metal salts) in the formation-"of aryl ether acid derivatives are the halogenated monobasic aliphatic acids such as aceticgbutyric, octoic, palmitic, stearic, naph- "'then'ic, etc.; polybasic acids such as maleic, suc- 'cinic, adipic, etc.; and aromatic acids such as benzoic,-' phthalic, cinnamic, furoic, etc. Both aliphatic and aromatic acids may also carry substituents such, for example, as keto, nitro, amin ihydroxyfgroups and the like.

'Ifl'ie s'ulfidesof'the alkylated'aryl ether acids are obtaifiedbyt dissolving the alkylated aryl ether' acid in''af suitable solvent such as carbon pepzehe, chlorbenzene, ethylene dip '"Stoddard"Solvent or the like. The t emr ierature ofthe solution may be brought up j-t'o'jabout 100? F. and the'sulfur halide or mix- ?t'uie o f sulfur halides added in the ratio of from aboutVg; to 1 mol of sulfur halide per mol of 'tlie acidlf The addition of' the sulfur halide 'shouldjb'e sufficientlyj slow' to prevent the tem- "p;erature substantially exceeding 100 F. and the ""inixturefmay be held at that temperature for about one h'our to complete the formation of "thesul'fur derivative. Hydrogen chloride is evolved in the reaction, resulting in fixation of the'";"siil fur in the aryl nucleus. -As regards the "temperature ofthe reaction, it is to be understood that'thefreaction can be carried out at 'vari'ous'temperatures from room temperature upfto the bciling'point of the solvent, but it is preferable for obtaining light-colored products that'the'temp'erature be not too high. The mixture is water wa'shed to remove dissolved hydro- "chloricacid; F I

"Wlie'n" the ayk'ylated aryl ether acid starting material"foi":sulfur condensation is obtained as the alkali carboxylate or alkali'metal salt, the "corresponding sulfide-"derivatives can be obtainedby-reacting' with sulfur halide without first liberatingthe free acid and in this case free B01 is not-evolved unless an amount of sulfur halide in excess of the sodium content is used, the HCl being-converted to sodium chloride by --reaction' with the carboxylate 1 alkali, thereby *libe'ra'ting' thefree alkylated ar'yl ether acid. When the-alkali salt'is used as an initial reactant; the procedure is in general the same as that described above except that solvents such as carbon disulflde' and ethylene dichloride must be replaced 'with solvents such as alcohol, benzene,

ing agents contemplated by the invention will appear from the following examples.

EXAMPLE ONE WAX-PHENOXY Acrzrrc ACID DISULFIDE A solution of 127.5 grams of monochloracetic acid in 100 cc. of anhydrous ethanol'was converted to sodium chloracetate by adding thereto a standard alcohol solution of sodium hydroxide, maintaining the temperature of thereaction mixture at about 100 F. This sodium chloracetate mixture was then added to a solution of 200 grams of wax-sodium phenate (3-16) in 600 grams of mineral oil (oil of Say. vis. of 67 sec. at 210 F.), and the mixture was stirred at 150 F. during a 2-hour period to form the wax-substituted phenoxy sodium acetate. The mixture was then sulfurized by lowering the temperature to about 100 F. and adding with rapid stirring 19.7 grams of sulfur monochloride at a rate sufliciently slow to avoid appreciable rise in temperature of the mixture by-the heat of reaction developed, The mixture was then stirred at this temperature about one hourto complete the sulfurization, followed by distilling the alcohol and water-washing the mixture until the aqueous extract was neutral. All traces of alcohol and water were then removed by steam-treating the mixture at about 300 F. to obtain thefinished product, which was approximately a A blend in mineral oil.

EXAMPLE TWO WAX-PHENOXY BENZOIC AcIn Drsrmrrnr:

.uct. The-free acid was then diluted with one volume of chlorbenzene and neutralized by adding one equivalent of sodium butylate and heating to about 200 F. for one hour before sulfurizing. The sulfurization was carried out by addin g'9.8 grams of sulfur monochloride at F. at rate sufiiciently slow to avoid appreciable temperature rise by the heat of reaction, and stir-ring one hour at this temperature to complete the sulfurization, whereby the wax-phenoxy benzoic aciddisulfide was formed. The

product was purified by water-washing the mix-.

EXAMPLE A POUR POINT DEPRESSION These tests were conducted with a motor oil having a Saybolt viscosity of 67 seconds at 210 F. and a pour pointof +20 F. The pour points The results of such tests are Table I A. S. T. M. pour point Addition agent %de- Ma% dedepressant pressant pressant Wax-phenoxy acetic acid di- F. F. F.

sulfide (3-16) +20 10 20 Wax-phenoxy benzoic acid disulfide (3-16) +20 -10 i EXAMPLE B Vrscosrry INDEX IMPROVEMENT The data listed in Table II below showing the efiectiveness of typical addition agents contemplated herein for improving viscosity index (V. I.) were obtained in the conventional manner from the Saybolt viscosity (Say. vis.) of the oil and the oil blends at 100 F. and 210 F. The oil used was a viscous mineral oil of the lubricant type.

EXAMPLE C OXIDATION INHIBITION In addition to the foregoing tests I have also made comparative tests between an oil and an oil blend containing representative improving agents of the type contemplated herein to determine the comparative behavior of the unblended oil and the improved oil under actual operating conditions. The tests were carried out in a single cylinder Lauson engine operated continuously over a time interval of 16 hours with the cooling medium held at a temperature of about 212 F. and the oil temperature held at about 280 F. The engine was operated at a speed of about 1830 R. P. M.

The oil used in the test was a lubricating oil stock of 45 seconds Saybolt viscosity at 210 F.

and the conditions observed were:

a. The amount of naphtha insoluble material formed in the oil.

12. The neutralization number or acidity (N. N.) of the oil.

0. The S. U. V. of the oil before and after the test.

In running these tests, comparative runs were made with a sample of the blank oil and a sample of oil containing the-addition agent. In Table III below the blank oil sample is indicated by A; and the oil with the addition agent used in the corresponding run is indicated by B. The oil blend B contained as addition agent:

wax-phenoxy aceticacid disulfide (316) Table III Per cent S U. V. at 011 N. N. naphtha 210 F- insolubles The amount of improving agent used in the oil may be varied, depending upon the character of the oil with which it is blended and the properties desired in the final oil composition. The sulfides of alkylated aryl ether acids contemplated herein may be used in amounts ranging from per cent to 10 per cent, and in general mineral oil compositions or the desired improved properties may be obtained with amounts in the neighborhood of 1 percent by weight.

It is to be understood that while I have described certain preierred procedures which may be followed in the preparation of the sulfides of alkylated aryl ether acids contemplated herein as oil-improving agents and have referred .to various representative constituents of these improving agents, such procedures and constituents are for illustrative purposes only. The invention, therefore, is not to be considered as limited by the specific examples given but includes Within its scope such changes and modifications as fairly come within the spirit or the appended claims.

I claim:

1. An miproved mineral oil composition comprising a mineral oil having admixed therewith in minor proportion an oil miscible condensation product characterized by at least two and nuclei, each of which is substituted with at least one mineral-oir-solubihzing alkyl group and with at least one-ether carboxyiic acid group, the said characterizing nuclei being interconnected by at least one atom oi'an element selected from the group consisting oi sulfur, selenium and tellurium.

2. An improved mineral oil composition comprising a mineral oil having admixed therewith in minor proportion an oil miscible condensation product characterized by at least two aryl nuclei, each of which is substituted with at least one alkyl group and with at least one other carboxylic acid group, the said characterizing nuclei being interconnected by at least one atom of an element selected Irom the group consisting oi sulfur, selenium and teilurium, the said aikyl substituents being aliphatic hydrocarbon groups of at least twenty carbon atoms.

3. An improved mineral oil composition comprising a rrnneral oil having admixed therewith in minor proportion an oil miscible condensation product characterized by at least two aryl nuclei, each of which is substituted with at least one alkyl group and with at least one ether carboxylic acid group, the said characterizing nuclei bein interconnected by at least one atom of an element -.product characterized by at least two aryl nuclei,

each of which is substituted with at least one mineral-oil-solubilizing alkyl group and with at least one ether carboxylic acid group, the said characterizing nuclei being interconnected by at least one atom of sulfur.

5. The composition of claim 4 in which the alkyl substituents correspond to the aliphatic hydrocarbon compounds which characterize petroleum wax.

6. The composition of claim 4 in which the alkyl substituents correspond to the aliphatic hydrocarbon compounds which characterize petroleum wax and in which the aryl nuclei are interconnected by a single atom of sulfur.

'7. The composition of claim 4 in which the alkyl substituents correspond to the aliphatic hydrocarbon compounds which characterize petroleum wax and in which the aryl nuclei are interconnected by two atoms only of sulfur.

-8. The composition of claim 4 in which the alkyl substituents correspond to the aliphatic hydrocarbon compounds which characterize petroleum wax and in which the ether carboxylic acid group is an ether aliphatic carboxylic acid group.

9. The composition of claim 4 in which the alkyl substituents correspond to the aliphatic hydrocarbon compounds of petroleum wax and in which the ether carboxylic acid group is an ether aromatic carboxylic acid group.

10. The composition of claim 4 in which the alkyl substituents correspond to the aliphatic hydrocarbon compounds which characterize petroleum wax and in which the aryl nuclei are phenyl nuclei and in which the ether carboxylic acid group is an ether acetic acid group and in which the phenyl nuclei are interconnected by two atoms only of sulfur.

11. The composition of claim 4 in which the .alkyl substituents correspond to the aliphatic mula.

0.2.0001; I-ozcoon n-'r-z..- 'r--n t. l Ll.

in which T represents an aromatic nucleus; R represents at least one oil-solubilizing alkyl group; O.Z.COOH represents an ether acid group wherein Z represents a radical selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals; Y is selected from the group consisting of hydrogen, hydroxyl, ester, alkyl sulfide, aryl sulfide, keto, alkoxy, aroxy, ether alcohol, aldehyde, thioaldehyde, oxime, amido, thioamido, carbamido, aralkyl, halogen, nitroso, amino, nitrosamino, amidino, imino, N-thio, diazo, hydrozino, syano, azoxy, azo, and hydrazo radicals; b represents the number of Ys and is equal to zero or a whole number corresponding to available hydrogens on the nucleus T not substituted with R, O.Z.COOH and Zn; 2 represents an element selected from the group consisting of sulfur, selenium, and tellurium; and n represents a whole number from one to four.

13. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a condensation compound characterized by having at least once therein the grouping corresponding to the general formula in which T represents an aromatic nucleus; R represents at least one alkyl group having at least twenty carbon atoms; O.Z.COOH represents an ether acid group wherein Z represents a radical selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals; Y is selected from the group consisting of hydrogen, hydroxyl, ester, keto, alkoxy, alkyl sulfide, aryl sulfide, aroxy, ether alcohol, aldehyde, thioaldehyde, oxime, amide, thioamido, carbamido, aralkyl, aryl, alkaryl, halogen, nitroso, amino, nitrosamino, amidino, imino, N-thio, diazo, hydrazino, cyano, azoxy, azo, and hydrazo radicals; b represents the number of Y substituents and is equal to zero 01' a whole number corresponding to available hydrogens on the nucleus T not substituted with R, O.Z.COOH and Zn; 2 represents an element selected from the group consisting of sulfur, selenium, and tellurium; and n represents a whole number from one to four.

ORLAND M. RE'IFF.

CERTIFICATE OF CORRECTION. Patent No. 2,526, 96. 4 Au ust 10, 191

ORLAND M. REIFF.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 11., sec- 0nd column, line 52, before the word "rate" insert --a-; page 5, second column, line 67, claim 5, before "in" insert --contained-; page 6, second column, line 12, claim 12, for "hydrozino syano, read -hydrazino, cya'no,-; and that the said Letters Patent should be read with this cor-. rection therein that the same may conform to the record of the casein the Patent Office,

Signed and sealed this llpth day of September, A. D. 19h}.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

